对亚甲基苯醌类衍生物的合成研究
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摘要
以2,6-二叔丁基苯酚和芳基甲醛为原料,甲苯为溶剂,哌啶为碱制备对亚甲基苯醌类衍生物,使用质谱(MS)、核磁共振光谱(~1H NMR)对所得化合物进行结构表征.通过单因素试验得出了制备此类化合物的最佳工艺条件:n(2,6-二叔丁基苯酚)∶n(苯甲醛)=1.2∶1,溶剂为甲苯,反应时间为12 h,反应温度为110℃.
Para-quinone methides were prepared by using 2,6-Di-tert-butyl phenol and aryl formaldehyde as raw materials, toluene as solvent and piperidine as base, and characterized by 1 H NMR spectra and MS. At the same time, the optimum conditions of process was achieved by discussing the factors. The optimum processing conditions are as follows: the molar radio of 2,6-Di-tert-butyl phenol and formaldehyde benzene is 1.2 ∶1,the solvent is toluene,reaction time is 12 h and the reaction temperature is 110 ℃.
Para-quinone methides were prepared by using 2,6-Di-tert-butyl phenol and aryl formaldehyde as raw materials, toluene as solvent and piperidine as base, and characterized by 1 H NMR spectra and MS. At the same time, the optimum conditions of process was achieved by discussing the factors. The optimum processing conditions are as follows: the molar radio of 2,6-Di-tert-butyl phenol and formaldehyde benzene is 1.2 ∶1,the solvent is toluene,reaction time is 12 h and the reaction temperature is 110 ℃.
引文
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[2]LóPEZ A,PARRA A,JARAVA-BARRERA C.Copper-catalyzed silylation of p-quinone methides:new entry to dibenzylic silanes[J].Chemical Communication,2015,51(100):17684-17687.DOI:10.1039/C5CC06653K.
[3]JANSEN R,GERTH K,STEINMETZ H,et al.Elansolid A3,a unique p-quinone methide antibiotic from chitinophaga sancti[J].Chemistry-A European Journal,2011,17(28),7739-7745.DOI:10.1002/chem.201100457.
[4]ZHANG H M,SRIDAR C,AMUNUGAMA H,et al.Polymorphic variants of cytochrome P450 2B6(CYP2B6.4-CYP2B6.9)exhibit altered rates of metabolism for bupropion and efavirenz:a charge-reversal mutation in the K139E variant(CYP2B6.8)impairs formation of a functional cytochrome p450-reductase complex[J].The Journal of Pharmacology and Experimental Therapeutics,2011,338(3):803-809.DOI:10.1124/jpet.111.183111.
[5]ZHOU Q B,KENNETH D T.Phosphodiester alkylation with a quinine methide[J].The Journal of Organic Chemistry,1999,64(8):2847-2851.DOI:10.1021/jo9823745.
[6]WANG Z,WONG Y F,SUN J.Catalytic asymmetric1,6-conjugate addition of para-quinone methides:formation of all-carbon quaternary stereocenters[J].Angewandte Chemie,2015,54(46):13711-13715.DOI:10.1002/anie.201506701.
[7]ZHANG X Z,GAN K J,LIU X X,et al.Enantioselective synthesis of functionalized 4-aryl hydrocoumarins and 4-aryl hydroquinolin-2-ones via intramolecular vinylogous rauhut-currier reaction of para-quinone methides[J].Organic Letters,2017,19(12):3207-3210.DOI:10.1021/acs.orglett.7b01331.
[8]ZHAO K,ZHI Y,SHU T,et al.Organocatalytic domino oxa-michael/1,6-addition reactions:asymmetric synthesis of chromans bearing oxindole scaffolds[J].Angewandte Chemie International Edition,2016,55(39):12104-12108.DOI:10.1002/anie.201606947.
[9]WANG Z B,WONG Y F,SUN J W.Catalytic asymmetric 1,6-conjugate addition of para-quinone methides:formation of all-carbon quaternary stereocenters[J].Angewandte Chemie International Edition,2015,54(46):13711-13714.DOI:10.1002/anie.201506701.
[10]GE L,LU X,CHENG C,et al.Amide-phosphonium salt as bifunctional phase transfer catalyst for asymmetric 1,6-addition of malonate esters to para-quinone methides[J].The Journal of Organic Chemistry,2016,81(19):9315-9325.DOI:10.1021/acs.joc.6b01906.
[11]ZHANG Z P,DONG N,LI X.Bismuth-catalyzed allylation of para-quinone methides[J].Chemical Communications,2017,53(7):1301-1304.DOI:10.1039/c6cc06605d.
[12]RICHTER D,HAMPEL N,SINGER T,et al.Synthesis and characterization of novel quinine methides:reference electrophiles for the construction of nucleophilicity scales[J].European Journal of Organic Chemistry,2009(19):3203-3211.DOI:10.1002/ejoc.200900299.
[13]陆鸿飞,张亮泽,唐丛焕,等.微波合成6-氯-2,3,5-三-o-乙酰基鸟苷[J].江苏科技大学学报(自然科学版),2010,24(4):391-394.DOI:10.3969/j.issn.1673-4807.2010.04.018.LU Hongfei,ZHANG Liangze,TANG Conghuan,et al.Microwave synthesis of 6-chloro-2 7,3 7,5’-tri-D-acetylguanosine[J].Journal of Jiangsu University of Science and Technology(Natural Science Edition),2010,24(4):391-394.DOI:10.3969/j.issn.1673-4807.2010.04.018.(in Chinese)